DE102019119059A1 - toner - Google Patents

Abstract

A toner comprising a toner particle containing a toner base particle and an organosilicon polymer on a surface of the toner base particle, the organosilicon polymer forming protruding portions having a certain structure on the surface of the toner base particle, and in the toner cross section when the protrusion width w is the length of the segment is where a protruding portion and the toner base particle form a continuous interface, the protrusion diameter D is the maximum length of a protruding portion, and the protrusion height H is the length from the tip of the protruding portion to the line along the circumference of the toner base particle surface , the numerical portion of these protruding sections with a ratio D / w of the protruding diameter D to the protruding width w from 0.33 to 0.80, at least 70% by number.

Description

Technical field

The present invention relates to the toner for developing the electrostatic charge image used in image forming devices such as electrophotographic devices, electrostatic printing devices, etc.

Description of the prior art

Laser printers and copiers are typical examples of devices based on an electrophotographic system that use toners. In recent years, the color scheme has developed dramatically and there are higher quality demands on the image quality. Improvements in transferability are a problem for toner-based electrophotography. For example, toner may remain on the photosensitive member (untransferred toner) if it is on the photosensitive member, i.e. the electrostatic image carrier element, formed toner image is transferred to the transfer material during the transfer step.

It is well known that reducing the adhesive force of the toner against the electrostatic image bearing member improves the transferability of the toner. Attaching an external additive to the toner particle surface is an example of means for reducing the adhesion force of toner. In particular, in a method known to improve transfer efficiency, the physical adhesive force between the toner and electrostatic image bearing member is reduced by a spacer effect that is produced by adding a spherical external additive with a large particle diameter.

However, while this is effective as a method of improving transfer efficiency, large-diameter spherical external additives undergo migration, peeling and embedding due to the long-term image output and can then no longer function as spacers. As a result, it was difficult to stably achieve the expected effect of improving transfer efficiency.

In the JP 2009-036 980 A proposed a method in which the migration and detachment of external additives is suppressed by semi-embedding an external additive with a large diameter.

2008 - 257 217 A, on the other hand, proposes a process in which the detachment and embedding is suppressed by the use of an external additive with a large diameter and hemispherical shape.

In order to improve the transferability by methods other than the external addition, extensive studies have also been carried out on methods in which the toner particle surface is coated with an organosilicon compound.

As an example of the ideas in the art of coating the toner particle surface with a silicon compound, the disclosure discloses JP 2001-075 304 A. a process for producing a polymerized toner, the process being characterized by the addition of a silane coupling agent to the reaction system.

A method using the combination of an external large diameter additive with a silane coupling agent is disclosed in US Pat JP 2017 - 138 462 A proposed. This method has made it possible to control the roughness of the toner particle surface while immobilizing the large-diameter external additive on the toner particle surface with the silane coupling agent. As a result, the migration, detachment and embedding of the external additive with a large diameter can be suppressed and high transferability can be maintained in the long term.

Summary of the invention

By achieving a semi-embedding of an external additive with a large diameter, the invention in FIG JP 2009-036 980 A suppression of migration and detachment of the external additive with a large diameter and therefore enables the spacer effect to be maintained in the long term. However, it was found that embedding in the second half of the durability test is accelerated by half-embedding.

In addition, the use of a large diameter hemispherical external additive suppresses JP 2008 - 257 217 A migration and embedding of the large diameter external additive, thus enabling long-term preservation of the spacer effect. However, it has been found that it is difficult to achieve uniform immobilization of the large diameter external additive on the toner particle surface by this method, and consequently maintaining the transfer efficiency improving effect to further extend the life is problematic.

With both JP 2009-036 980 A as well as JP 2008 - 257 217 A it was also found that there was a problem with the uniformity of immobilization of the large-diameter external additive by using dry external addition. So in the case of JP 2009-036 980 A migration and detachment are not completely suppressed and the elements may be contaminated by the detached external additive with a large diameter. The contamination of the elements is also at JP 2008 - 257 217 A generated because migration and detachment are facilitated when the protruding portion faces the hemispherical shape of the toner particle surface.

With the JP 2001-075 304 A. on the other hand, high transferability was not achieved due to an insufficient coating by the silicon compound due to an insufficient amount of deposition of the silane compound on the toner particle surface.

With the JP 2017 - 138 462 A It has been found that since the external large diameter additive used is a sphere, the load received by the normal direction toner will ultimately be concentrated at a single point on the large diameter external additive and a problem with respect to the ability arises to resist embedding. This is therefore unsatisfactory in order to achieve a further increase in the service life.

An object of the present invention is to solve these problems. That is, the present invention provides a toner which has high transferability and is resistant to change even in long-term use, and thus maintains high transferability.

As a result of intensive studies, the present inventors discovered that a toner that solves the above problems is obtained by forming protruding portions on the toner particle surface and controlling the shape of these protruding portions.

Thus, the present invention relates to a toner comprising a toner particle containing a toner base particle and an organosilicon polymer on the surface of the toner base particle, wherein
the organosilicon polymer has the structure represented by the following formula (1);
the organosilicon polymer forms protruded portions on the surface of the toner base particle; and
in a flat image provided by observing the toner cross section with a scanning transmission electron microscope STEM, drawing a line along the circumference of the toner base particle surface and converting based on this line along the circumference, and
assuming that the length of the line along the circumference for a segment where a protruding portion and the toner base particle form a continuous interface is taken as the protrusion width w that the maximum length of a protruding portion in the direction perpendicular to the overhang width w is taken as the overhang diameter D and the length in the line segment forming the overhang diameter D is taken from the tip of a projecting portion to the line along the circumference as the overhang height H. .
the numerical component P (D / w), in projecting sections with a projecting height H of 40 nm to 300 nm, of projecting sections with a ratio D / w of the projecting diameter D to the projecting width w from 0.33 to 0.80, at least 70% by number. R-SiO _3/2 (1)

In the formula, R represents an alkyl group having 1 to 6 carbon atoms or a phenyl group.

The present invention can thus provide a toner which has high transferability and is resistant to changes even in long-term use and thus maintains high transferability.

Further features of the present invention will become apparent from the following description of exemplary embodiments with reference to the accompanying drawings.

list of figures

• 1 Figure 12 is a schematic diagram of a toner cross-section as observed with a STEM;
• 2 Fig. 11 is a schematic diagram showing a methodology for measuring the supernatant shape on the toner;
• 3 Fig. 11 is a schematic diagram showing a methodology for measuring the supernatant shape on the toner; and
• 4 Fig. 11 is a schematic diagram showing a methodology for measuring the supernatant shape on the toner.

Description of the embodiments

Embodiments of the present invention are described below, but the present invention is not limited to or by the following embodiments.

Unless expressly stated otherwise, the terms “from XX to YY” and “XX to YY”, which represent numerical ranges of values, in the present invention refer to numerical ranges of values that include the lower and upper bounds, which are the end points.

The toner according to the present invention relates to a toner comprising a toner particle containing a toner base particle and an organosilicon polymer on the surface of the toner base particle, wherein
the organosilicon polymer has the structure represented by the following formula (1);
the organosilicon polymer forms protruding portions on the surface of the toner base particle; and
in a flat image provided by observing the toner cross section with a scanning transmission electron microscope STEM, drawing a line along the circumference of the toner base particle surface and converting based on this line along the circumference, and
assuming that the length of the line along the circumference for a segment where a protruding portion and the toner base particle form a continuous interface is taken as the protrusion width w, the maximum length of a protruding portion in the direction perpendicular to the protrusion Width w is taken as the projection diameter D and that the length in the line segment which forms the projection diameter D is taken from the tip of a projecting section to the line along the circumference as the projection height H,
the numerical component P (D / w), in projecting sections with a projecting height H of 40 nm to 300 nm, of projecting sections with a ratio D / w of the projecting diameter D to the projecting width w from 0.33 to 0.80, at least 70% by number. R-SiO _3/2 (1)

In the formula, R represents an alkyl group having 1 to 6 carbon atoms or a phenyl group.

The above conditions and requirements are described in detail below.

The toner according to the present invention has protruding portions on the toner particle surface containing an organosilicon polymer. These protruding portions are set in surface contact with the surface of the toner base particle. It is to be expected that this surface contact will have a considerable inhibiting influence on the migration, detachment and embedding of the protruding sections. STEM observations of the toner cross section were made to show the degree of surface contact. 1 to 4 provide schematic diagrams of these protruding portions on a toner particle.

In the 1 indicated 1 is a STEM image. This image shows about a quarter section of a toner particle, 2 being a toner base particle, 3 being the surface of the toner base particle, and 4 being a protruding section. In 2 to 4 5 is the protrusion width w, 6 is the protrusion diameter D and 7 is the protrusion height H.

An image of the toner cross section is observed and a line is drawn along the circumference of the surface of the toner base particle. The conversion to a flat image is based on this line along the circumference. In this flat image, the protrusion width w is taken as the length of the line along the circumference of the segment where a protruding portion and the toner base particle form a continuous interface. The protrusion diameter D is taken as the maximum length of a protruding portion in the direction perpendicular to the protrusion width w, and the protrusion height H is taken as the length in the line segment that constitutes the protrusion diameter D from the tip of the protrusion Section adopted to the line along the circumference.

The protrusion diameter D and the protrusion height H are in 2 and 4 same, while the excess diameter D in 3 is greater than the overhang height H.

4 Fig. 3 schematically represents the immobilized state for a particle similar to a bowl-shaped particle in which the central part of a hemispherical particle is recessed, as obtained by crushing and dividing a hollow particle. In 4 the supernatant width w is the sum of the lengths of the organosilicon compound in contact with the surface of the toner base particle. The protrusion width w in 4 is thus the sum of W1 and W2.

It was discovered that the protruding sections are resistant to migration, detachment and embedding when the supernatant shape for the protruding sections of the organosilicon compound is based on the above definitions the ratio D / w of the protruding diameter D to the protruding width w of 0.33 to 0.80. That is, it has been discovered that excellent transferability that withstands prolongation of life is demonstrated when the numerical portion P (D / w) for protruding portions with a supernatant height H of 40 nm to 300 nm is from protruding sections with a ratio D / w of 0.33 to 0.80, at least 70% by number.

It is believed that transferability is improved by creating a spacer effect between the toner base particle surface and the transfer element due to protruding portions of at least 40 nm. On the other hand, it is believed that a significant inhibitory effect on migration, peeling, and embedding occurs during a durability assessment due to protruding portions that are not more than 300 nm.

It was found that if the numerical fraction P (D / w) is at least 70% by number for the fraction for protruding portions from 40 nm to 300 nm, a strong inhibitory effect on the contamination of the elements is also shown during the durability test while maintaining portability. P (D / w) is preferably at least 75% by number and is more preferably at least 80% by number. While there is no particular limitation on the upper limit, it is preferably not more than 99% by number and more preferably is not more than 98% by number.

In addition, when observing the toner cross section using a scanning transmission electron microscope STEM, assuming that the width of the flat image (length of the line along the circumference of the toner base particle surface) is taken as the circumferential length L and the sum of the protruding widths w of the protruding portions a protrusion height H of 40 nm to 300 nm of the protruding portions of the organosilicon polymer present in the flat image is taken as Σw, Σw / L preferably from 0.30 to 0.90.

A better transferability and a better inhibitory effect on the contamination of the elements is achieved if Σw / L is at least 0.30, and a superior transferability is achieved if Σw / L is not more than 0.90. Σw / L is more preferred from 0.45 to 0.80.

The fixing ratio of the organosilicon polymer for the toner is preferably at least 80% by mass. A fixation ratio of at least 80% by mass enables better durability of the transferability and an inhibiting effect on the contamination of the elements with prolonged use. The fixing ratio is preferably at least 90% by mass, and more preferably at least 95% by mass. The upper limit, however, is not particularly limited, but is preferably not more than 99 mass% and more preferably is not more than 98 mass%. This fixation ratio can be controlled, for example, by the following factors during the addition and polymerization of the organosilicon compound: addition ratio of the organosilicon compound, reaction temperature, reaction time, pH during the reaction and time of pH adjustment.

In addition, H80 is preferably at least 65 nm from the viewpoint of an even better transferability, and if a cumulative distribution of the protrusion height H is created for the protruding sections with a protrusion height H of 40 nm to 300 nm, H80 the protrusion Height is 80% by number for the accumulation of the overhang height H from the small side. At least 75 nm are more preferred. The upper limit is not particularly limited, but is preferably not more than 120 nm and more preferably is not more than 100 nm.

The number-average diameter for the protrusion diameter R is preferably 20 nm to 80 nm, the protrusion diameter R being the maximum diameter of the protruding section made of organosilicon polymer while observing the toner with a scanning electron microscope SEM. From 35 nm to 60 nm is more preferred. The occurrence of contamination of elements is prevented in this area.

The toner contains an organosilicon polymer having the structure represented by the following formula (1). R-SiO _3/2 (1) (In the formula, R represents an alkyl group having 1 to 6 carbon atoms or a phenyl group.)

In the organosilicon polymer having the structure represented by the formula (1), one of the four valences of the Si atom is bonded to R and the remaining three are bonded to an O atom. The O atom is in a state in which its two valences are each bound to Si, which creates a siloxane bond (Si-O-Si). If one looks at the Si atom and the O atom at the level of the organosilicon polymer, they are represented by -SiO _3/2 , since three O atoms are present for two Si atoms. The -SiO _3/2 structure of this organosilicon polymer is believed to have properties similar to that of silicon dioxide (SiO ₂ ), which consists of a variety of siloxane bonds.

The R in the substructure represented by the formula (1) is preferably an alkyl group having 1 to 6 carbon atoms and is more preferably an alkyl group having 1 to 3 carbon atoms.

Preferred examples of the alkyl group having 1 to 3 carbon atoms are the methyl group, the ethyl group and the propyl group. R is more preferably the methyl group.

(In Formel (Z) stellt R₁ eine Kohlenwasserstoffgruppe (bevorzugt eine Alkylgruppe) mit 1 bis 6 Kohlenstoffatomen dar, und R₂, R₃ und R₄ stellen jeweils unabhängig voneinander ein Halogenatom, eine Hydroxygruppe, eine Acetoxygruppe oder eine Alkoxygruppe dar.)The organosilicon polymer is preferably a condensation polymer of an organosilicon compound having the structure represented by the following formula (Z).

(In formula (Z), R _{1 represents} a hydrocarbon group (preferably an alkyl group) having 1 to 6 carbon atoms, and R ₂ , R ₃ and R ₄ each independently represent a halogen atom, a hydroxyl group, an acetoxy group or an alkoxy group.)

R ₁ is preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms and is more preferably the methyl group.

R ₂ , R ₃ and R ₄ each independently represent a halogen atom, a hydroxy group, an acetoxy group or an alkoxy group (hereinafter also referred to as a reactive group). These reactive groups undergo hydrolysis, addition polymerization and condensation polymerization, which creates a cross-linked structure.

The hydrolysis is gentle at room temperature, and from the viewpoint of the deposition behavior on the surface of the toner base particle, an alkoxy group having 1 to 3 carbons is preferred, with the methoxy group and the ethoxy group being more preferred.

The hydrolysis, addition polymerization and condensation polymerization of R ₂ , R ₃ and R ₄ can be controlled using the reaction temperature, the reaction time, the reaction solvent and the pH. A single organosilicon compound with three reactive groups (R ₂ , R ₃ and R ₄ ) in the individual molecule, with the exception of R ₁ in the above formula (Z) (hereinafter also referred to as trifunctional silane), or a combination of one A variety of such organosilicon compounds can be used to obtain the organosilicon polymer used in the present invention.

• trifunktionelle Methylsilane, wie etwa Methyltrimethoxysilan, Methyltriethoxysilan, Methyldiethoxymethoxysilan, Methylethoxydimethoxysilan, Methyltrichlorsilan, Methylmethoxydichlorsilan, Methylethoxydichlorsilan, Methyldimethoxychlorsilan, Methylmethoxyethoxychlorsilan, Methyldiethoxychlorsilan, Methyltriacetoxysilan, Methyldiacetoxymethoxysilan, Methyldiacetoxyethoxysilan, Methylacetoxydimethoxysilan, Methylacetoxymethoxyethoxysilan, Methylacetoxydiethoxysilan, Methyltrihydroxysilan, Methylmethoxydihydroxysilan, Methylethoxydihydroxysilan, Methyldimethoxyhydroxysilan, Methylethoxymethoxyhydroxysilan und Methyldiethoxyhydroxysilan;
• trifunktionelle Silane, wie etwa Ethyltrimethoxysilan, Ethyltriethoxysilan, Ethyltrichlorsilan, Ethyltriacetoxysilan, Ethyltrihydroxysilan, Propyltrimethoxysilan, Propyltriethoxysilan, Propyltrichlorsilan, Propyltriacetoxysilan, Propyltrihydroxysilan, Butyltrimethoxysilan, Butyltriethoxysilan, Butyltrichlorsilan, Butyltriacetoxysilan, Butyltrihydroxysilan, Hexyltrimethoxysilan, Hexyltriethoxysilan, Hexyltrichlorsilan, Hexyltriacetoxysilan und Hexyltrihydroxysilan; und
• trifunktionelle Phenylsilane, wie etwa Phenyltrimethoxysilan, Phenyltriethoxysilan, Phenyltrichlorsilan, Phenyltriacetoxysilan und Phenyltrihydroxysilan.

The following are examples of compounds having the formula (Z):

• trifunctional methylsilane, such as methyltrimethoxysilane, methyltriethoxysilane, Methyldiethoxymethoxysilan, Methylethoxydimethoxysilan, methyltrichlorosilane, Methylmethoxydichlorsilan, Methylethoxydichlorsilan, methyldimethoxychlorosilane, Methylmethoxyethoxychlorsilan, Methyldiethoxychlorsilan, methyltriacetoxysilane, Methyldiacetoxymethoxysilan, Methyldiacetoxyethoxysilan, Methylacetoxydimethoxysilan, Methylacetoxymethoxyethoxysilan, Methylacetoxydiethoxysilan, methyltrihydroxysilane, Methylmethoxydihydroxysilan, Methylethoxydihydroxysilan, Methyldimethoxyhydroxysilan, Methylethoxymethoxyhydroxysilan and Methyldiethoxyhydroxysilan;
• trifunctional silanes such as ethyltrimethoxysilane, ethyltriethoxysilane, ethyltrichlorosilane, ethyltriacetoxysilane, Ethyltrihydroxysilan, propyltrimethoxysilane, propyltriethoxysilane, propyltrichlorosilane, propyltriacetoxysilane, Propyltrihydroxysilan, butyltrimethoxysilane, butyltriethoxysilane, butyltrichlorosilane, Butyltriacetoxysilan, Butyltrihydroxysilan, hexyltrimethoxysilane, hexyltriethoxysilane, hexyltrichlorosilane, Hexyltriacetoxysilan and Hexyltrihydroxysilan; and
• trifunctional phenylsilanes such as phenyltrimethoxysilane, phenyltriethoxysilane, phenyltrichlorosilane, phenyltriacetoxysilane and phenyltrihydroxysilane.

• Dimethyldiethoxysilan, Tetraethoxysilan, Hexamethyldisilazan, 3-Aminopropyltrimethoxysilan, 3-Aminopropyltriethoxysilan, 3-(2-Aminoethyl)aminopropyltrimethoxysilan und 3-(2-Aminoethyl)aminopropyltriethoxysilan, und trifunktionelle Vinylsilane, wie etwa Vinyltriisocyanatosilan, Vinyltrimethoxysilan, Vinyltriethoxysilan, Vinyldiethoxymethoxysilan, Vinylethoxydimethoxysilan, Vinylethoxydihydroxysilan, Vinyldimethoxyhydroxysilan, Vinylethoxymethoxyhydroxysilan und Vinyldiethoxyhydroxysilan.

As far as the effect of the present invention is not impaired, an organosilicon polymer obtained by using the following in combination with the organosilicon compound having the structure represented by the formula (Z) can be used: an organosilicon compound having four reactive groups in each molecule (tetrafunctional Silane), an organosilicon compound with two reactive groups in each molecule (difunctional silane) or an organosilicon compound with one reactive group (monofunctional silane). Examples are as follows:

• Dimethyldiethoxysilane, tetraethoxysilane, hexamethyldisilazane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- (2-aminoethyl) aminopropyltrimethoxysilane and 3- (2-aminoethyl) aminopropyltriethoxysilane, and trifunctional vinyl silanes such as Vinyltriisocyanatosilan, vinyltrimethoxysilane, vinyltriethoxysilane, Vinyldiethoxymethoxysilan, Vinylethoxydimethoxysilan, Vinylethoxydihydroxysilan, Vinyldimethoxyhydroxysilane, vinylethoxymethoxyhydroxysilane and vinyldiethoxyhydroxysilane.

The content of the organosilicon polymer in the toner particle is preferably from 1.0 mass% to 10.0 mass%.

The following is an example of a preferred method of forming the supernatant shape on the toner particle surface as described above: dispersing a toner base particle in an aqueous medium to obtain a toner base particle dispersion, and then adding the organosilicon compound and causing the supernatant shape to form, to obtain a toner particle dispersion.

The solids concentration in the toner base particle dispersion is preferably set to from 25% by mass to 50% by mass. The temperature of the toner base particle dispersion is preferably set to at least 35 ° C in advance. In addition, the pH of the toner base particle dispersion is preferably adjusted to a pH that prevents the condensation from proceeding by the organosilicon compound. Since the pH value, which prevents the condensation by the organosilicon compound from progressing, varies with the respective substance, the pH is centered within ± 0.5 at which the reaction is most strongly prevented.

The use of an organosilicon compound which has undergone hydrolysis treatment is preferred. For example, the hydrolysis can be carried out beforehand in a separate vessel as a pretreatment for the organosilicon compound. The charge concentration for the hydrolysis using 100 parts by mass for the amount of the organosilicon compound is preferably from 40 parts by mass to 500 parts by mass, and more preferably 100 parts by mass to 400 parts by mass of water from which the ionic fraction has been removed, for example, deionized water or RO -Water. The conditions during the hydrolysis is preferably a pH of 2 to 7, a temperature of 15 ° C to 80 ° C and a time of 30 to 600 minutes.

The resulting hydrolysis solution is mixed with the toner base particle dispersion and adjusted to a pH suitable for the condensation (preferably 6 to 12 or 1 to 3, and more preferably 8 to 12). Formation of the supernatant form is facilitated by adjusting the amount of the hydrolysis solution to 5.0 parts by mass to 30.0 parts by mass of the organosilicon compound per 100 parts by mass of the toner base particle. The condensation temperature and time during the formation of the supernatant form are preferably kept at 35 ° C to 99 ° C for 60 minutes to 72 hours.

The pH is preferably set in two stages, taking into account the control of the supernatant shape on the toner particle surface. The supernatant form on the toner particle surface can be controlled by condensing the organosilicon compound with appropriate adjustment of the hold time before the pH adjustment and the hold time before the pH adjustment in the second step. For example, a hold for 0.5 hours to 1.5 hours is preferably carried out at a pH of 4.0 to 6.0, followed by a hold for 3.0 hours to 5.0 hours at a pH of 8.0 to 11.0. The supernatant shape can also be controlled by adjusting the condensation temperature for the organosilicon compound in the range of 35 ° C to 80 ° C.

For example, the overhang width w can be determined using e.g. the addition amount of the organosilicon compound, the reaction temperature, the reaction pH in the first stage and the reaction time can be controlled. For example, the overhang width tends to increase with increasing reaction time in the first stage.

The protrusion diameter D and the protrusion height H can be e.g. the addition amount of the organosilicon polymer, the reaction temperature and the pH of the second stage are controlled. For example, the supernatant diameter D and the supernatant height H tend to increase as the reaction pH increases in the second stage.

Specific toner manufacturing processes are described below, but are not intended to be a limitation to or by any limitation.

Preferably, the toner base particle is made in an aqueous medium and the organosilicon polymer-containing protruding portions are formed on the surface of the toner base particle.

The suspension polymerization method, the solution suspension method and the emulsion aggregation method are preferred methods for producing the toner base particles, with the suspension polymerization being more preferred among them. The suspension polymerization process facilitates uniform deposition of the organosilicon polymer on the surface of the toner base particle, supports excellent adhesion by the organosilicon polymer, and provides excellent environmental stability, excellent suppression of charge inversion components, and excellent durability of the foregoing in long-term use. The suspension polymerization process is described in more detail below.

The toner base particle is obtained in the suspension polymerization process by granulating, in an aqueous medium, a polymerizable monomer composition containing polymerizable monomer capable of producing a binder resin, and optional additives such as coloring agents, and then polymerizing the polymerizable monomer present in the polymerizable monomer composition.

The polymerizable monomer composition may also optionally contain a release agent as well as other resins. After the polymerization step, the particles produced can be washed and recovered by filtration using known methods. The temperature can be raised in the second half of the polymerization step. In order to remove unreacted polymerizable monomer and secondary products, part of the dispersion medium can also be distilled from the reaction system in the second half of the polymerization step or after the polymerization step has ended.

Preferably, the protruding portions of the organosilicon polymer are formed using the method described above and the toner base particle obtained thereby.

• Wachse auf Erdölbasis, wie etwa Paraffinwachse, mikrokristalline Wachse und Petrolatum, und Derivate davon; Montanwachs und Derivate davon; nach dem Fischer-Tropsch-Verfahren hergestellte Kohlenwasserstoffwachse und Derivate davon; Polyolefinwachse, wie etwa Polyethylen und Polypropylen, und Derivate davon; natürliche Wachse, wie etwa Carnaubawachs und Candelillawachs und deren Derivate; höhere aliphatische Alkohole; Fettsäuren, wie etwa Stearinsäure und Palmitinsäure und deren Säureamide, Ester und Ketone; hydriertes Rizinusöl und deren Derivate; sowie Pflanzenwachse, tierische Wachse und Silikonharze.

A release agent can be used in the toner. This release agent can be illustrated using the following examples:

• Petroleum-based waxes such as paraffin waxes, microcrystalline waxes and petrolatum, and derivatives thereof; Montan wax and derivatives thereof; Hydrocarbon waxes and derivatives thereof manufactured by the Fischer-Tropsch process; Polyolefin waxes such as polyethylene and polypropylene and derivatives thereof; natural waxes such as carnauba wax and candelilla wax and their derivatives; higher aliphatic alcohols; Fatty acids such as stearic acid and palmitic acid and their acid amides, esters and ketones; hydrogenated castor oil and its derivatives; as well as plant waxes, animal waxes and silicone resins.

The derivatives include oxides as well as block copolymers and graft modifications with vinyl monomers. A single release agent can be used, or a mixture of a variety of release agents can be used.

The release agent content, based on 100 parts by mass of the binder resin or the polymerizable monomer which produces the binder resin, is preferably from 2.0 parts by mass to 30.0 parts by mass.

• Homopolymere von Styrol oder ein Derivat davon, z.B. Polystyrol und Polyvinyltoluol; Styrolcopolymere, wie etwa Styrol-Propylen-Copolymer, Styrol-Vinyltoluol-Copolymer, Styrol-Vinylnaphthalin-Copolymer, Styrol-Methylacrylat-Copolymer, Styrol-Ethylacrylat-Copolymer, Styrol-Butylacrylat-Copolymer, Styrol-Octylacrylat-Copolymer, Styrol-Dimethylaminoethylacrylat-Copolymer, Styrol-Methylmethacrylat-Copolymer, Styrol-Ethylmethacrylat-Copolymer, Styrol-Butylmethacrylat-Copolymer, Styrol-Dimethylaminoethylmethacrylat, Styrol-Vinylmethanol-Copolymer, Styrol-Vinylethylether-Copolymer, Styrol-Vinylmethylketon-Copolymer, Styrol-Butadien-Copolymer, Styrol-Isopren-Copolymer, Styrol-Maleinsäure-Copolymer und Styrol-Maleatester-Copolymer; sowie Polymethylmethacrylat, Polybutylmethacrylat, Polyvinylacetat, Polyethylen, Polypropylen, Polyvinylbutyral, Silikonharze, Polyesterharze, Polyamidharze, Epoxidharze, Polyacrylharze, Kolophonium, modifiziertes Kolophonium, Terpenharze, Phenolharze, aliphatische Kohlenwasserstoffharze, alicyclische Kohlenwasserstoffharze und aromatische Erdölharze. Ein einzelnes davon kann verwendet werden, oder es kann eine Mischung aus mehreren verwendet werden.

For example, the following resins can be used as the other resins:

• Homopolymers of styrene or a derivative thereof, for example polystyrene and polyvinyltoluene; Styrene copolymers, such as styrene / propylene copolymer, styrene / vinyl toluene copolymer, styrene / vinyl naphthalene copolymer, styrene / methyl acrylate copolymer, styrene / ethyl acrylate copolymer, styrene / butyl acrylate copolymer, styrene / octyl acrylate copolymer, styrene / dimethylaminoethyl acrylate copolymer Copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-dimethylaminoethyl methacrylate, styrene-vinyl methanol copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene Isoprene copolymer, styrene-maleic acid copolymer and styrene-maleate ester copolymer; and polymethyl methacrylate, polybutyl methacrylate, polyvinyl acetate, polyethylene, polypropylene, polyvinyl butyral, silicone resins, polyester resins, polyamide resins, epoxy resins, polyacrylic resins, rosin, modified rosin, terpene resins, phenolic resins, aliphatic hydrocarbon resins, alicyclic hydrocarbon resins. A single one of them can be used, or a mixture of several can be used.

• Styrol; Styrolderivate, wie etwa α-Methylstyrol, β-Methylstyrol, o-Methylstyrol, m-Methylstyrol, p-Methylstyrol, 2,4-Dimethylstyrol, p-n-Butylstyrol, p-tert-Butylstyrol, p-n-Hexylstyrol, p-n-Octylstyrol, p-n-Nonylstyrol, p-n-Decylstyrol, p-n-Dodecylstyrol, p-Methoxystyrol und p-Phenylstyrol; polymerisierbare Acrylmonomere, wie etwa Methylacrylat, Ethylacrylat, n-Propylacrylat, Isopropylacrylat, n-Butylacrylat, Isobutylacrylat, tert-Butylacrylat, n-Amylacrylat, n-Hexylacrylat, 2-Ethylhexylacrylat, n-Octylacrylat, n-Nonylacrylat, Cyclohexylacrylat, Benzylacrylat, Dimethylphosphat-Ethylacrylat, Diethylphosphat-Ethylacrylat, Dibutylphosphat-Ethylacrylat und 2-Benzoyloxyethylacrylat; polymerisierbare Methacrylmonomere, wie etwa Methylmethacrylat, Ethylmethacrylat, n-Propylmethacrylat, Isopropylmethacrylat, n-Butylmethacrylat, Isobutylmethacrylat, tert-Butylmethacrylat, n-Amylmethacrylat, n-Hexylmethacrylat, 2-Ethylhexylmethacrylat, n-Octylmethacrylat, n-Nonylmethacrylat, Diethylphosphatmethacrylat und Dibutylphosphatethylmethacrylat; aliphatische Methylen-Monocarbonsäureester; Vinylester, wie etwa Vinylacetat, Vinylpropionat, Vinylbenzoat, Vinylbutyrat und Vinylformiat; Vinylether, wie etwa Vinylmethylether, Vinylethylether und Vinylisobutylether; sowie Vinylmethylketon, Vinylhexylketon und Vinylisopropylketon.

The following polymerizable vinyl monomers are advantageous examples of the polymerizable monomer:

• styrene; Styrene derivatives, such as, for example, α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn- Nonylstyrene, pn-decylstyrene, pn-dodecylstyrene, p-methoxystyrene and p-phenylstyrene; polymerizable acrylic monomers, such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2-ethyl hexyl acrylate, n-octyl acrylate, n-nyl acrylate, n-nyl acrylate Ethyl acrylate, diethyl phosphate ethyl acrylate, dibutyl phosphate ethyl acrylate and 2-benzoyloxyethyl acrylate; polymerizable methacrylic monomers, such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate methacrylate methacrylate methacrylate, diethyl methacrylate, aliphatic methylene monocarboxylic acid esters; Vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate, vinyl butyrate and vinyl formate; Vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether; as well as vinyl methyl ketone, vinyl hexyl ketone and vinyl isopropyl ketone.

Among these vinyl monomers, styrene, styrene derivatives, polymerizable acrylic monomers and polymerizable methacrylic monomers are preferred.

• Azo- und Diazopolymerisationsinitiatoren, wie etwa 2,2'-Azobis(2,4-divaleronitril), 2,2'-Azobisisobutyronitril, 1,1'-Azobis(cyclohexan-1-carbonitril), 2,2'-Azobis-4-methoxy-2,4-dimethylvaleronitril und Azobisisobutyronitril; und Peroxidpolymerisationsinitiatoren, wie etwa Benzoylperoxid, Methylethylketonperoxid, Diisopropylperoxycarbonat, Cumolhydroperoxid, 2,4-Dichlorbenzoylperoxid und Lauroylperoxid.

A polymerization initiator can be added to the polymerization of the polymerizable monomer. The following are examples of the polymerization initiator:

• Azo and diazo polymerization initiators such as 2,2'-azobis (2,4-divaleronitrile), 2,2'-azobisisobutyronitrile, 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis-4 -methoxy-2,4-dimethylvaleronitrile and azobisisobutyronitrile; and peroxide polymerization initiators such as benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxy carbonate, cumene hydroperoxide, 2,4-dichlorobenzoyl peroxide and lauroyl peroxide.

These polymerization initiators are preferably added at 0.5 parts by mass to 30.0 parts by mass per 100 parts by mass of the polymerizable monomer, and a single polymerization initiator can be used or a variety can be used in combination.

A chain transfer agent can be added to the polymerization of the polymerizable monomer to control the molecular weight of the binder resin that forms the toner base particle. The preferred addition amount is 0.001 parts by mass to 15,000 parts by mass per 100 parts by mass of the polymerizable monomer.

• Divinylbenzol, Bis(4-acryloxypolyethoxyphenyl)propan, Ethylenglykoldiacrylat, 1,3-Butylenglykoldiacrylat, 1,4-Butandioldiacrylat, 1,5-Pentandioldiacrylat, 1,6-Hexandioldiacrylat, Neopentylglykoldiacrylat, Diethylenglykoldiacrylat, Triethylenglykoldiacrylat, Tetraethylenglykoldiacrylat, die Diacrylate von Polyethylenglykol #200, #400 und #600, Dipropylenglykoldiacrylat, Polypropylenglykoldiacrylat, Polyester-Typ Diacrylate (MANDA, Nippon Kayaku Co., Ltd.) und Vernetzungsmittel, die durch die Änderung des Acrylats im vorhergehenden zu Methacrylat bereitgestellt werden.

A crosslinking agent can be added to the polymerization of the polymerizable monomer to control the molecular weight of the binder resin that forms the toner base particle. The following are examples:

• Divinylbenzene, bis (4-acryloxypolyethoxyphenyl) propane, ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, neopentylglycol diacrylate, diethylene glycol triethylene glycol, diacrylate diacrylate diacrylate diacrylate, , # 400 and # 600, dipropylene glycol diacrylate, polypropylene glycol diacrylate, polyester type diacrylates (MANDA, Nippon Kayaku Co., Ltd.) and crosslinking agents provided by changing the acrylate to methacrylate in the foregoing.

Polyfunctional crosslinking monomers can be illustrated by means of the following examples: pentaerythritol triacrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, oligoester acrylates and their methacrylates, 2,2-bis (4-methacryloxy.polyethoxyphenyl.) Propane, triallyltrimethyllateurate, triacrylylurate, diacriallyl triturate,

The preferred addition amount is 0.001 parts by mass to 15,000 parts by mass per 100 parts by mass of the polymerizable monomer.

• Tricalciumphosphat, Magnesiumphosphat, Zinkphosphat, Aluminiumphosphat, Calciumcarbonat, Magnesiumcarbonat, Calciumhydroxid, Magnesiumhydroxid, Aluminiumhydroxid, Calciummetasilikat, Calciumsulfat, Bariumsulfat, Bentonit, Silica und Aluminiumoxid.

When the medium used in the above suspension polymerization is an aqueous medium, the following can be used as a dispersion stabilizer for the particles of the polymerizable monomer composition:

• Tricalcium phosphate, magnesium phosphate, zinc phosphate, aluminum phosphate, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, bentonite, silica and aluminum oxide.

Examples of organic dispersants are: polyvinyl alcohol, gelatin, methyl cellulose, methyl hydroxypropyl cellulose, ethyl cellulose, the sodium salt of carboxymethyl cellulose and starch.

A commercially available nonionic, anionic or cationic surfactant can also be used. These surfactants are illustrated by the following examples: sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate and potassium stearate.

A colorant can be used in the toner; there are no particular restrictions on the colorant, and known colorants can be used.

The colorant content per 100 parts by mass of the binder resin or the polymerizable monomer that the binder resin can produce is preferably from 3.0 parts by mass to 15.0 parts by mass.

A charge control agent can be used during toner production, and a known charge control agent can be used. The addition amount of the charge control agent is preferably 0.01 part by mass to 10.00 parts by mass per 100 parts by mass of the binder resin or polymerizable monomer.

As such, the toner particle can be used as a toner, or any of various organic or inorganic fine powders can be added externally to the toner particle. In view of the durability when added to the toner particles, a particle diameter which is equal to or smaller than one tenth of the weight-average particle diameter of the toner particles is preferred for this organic or inorganic fine powder.

1. (1) Fließfähigkeit verleihende Mittel: Silica, Aluminiumoxid, Titanoxid, Carbon Black und fluorierter Kohlenstoff.
2. (2) Schleifmittel: Metalloxide (z.B. Strontiumtitanat, Ceroxid, Aluminiumoxid, Magnesiumoxid, Chromoxid), Nitride (z.B. Siliciumnitrid), Carbide (z.B. Siliciumcarbid), Metallsalze (z.B. Calciumsulfat, Bariumsulfat, Calciumcarbonat).
3. (3) Schmiermittel: Fluorharzpulver (z.B. Vinylidenfluorid, Polytetrafluorethylen), Metallsalze von Fettsäuren (z.B. Zinkstearat, Kalziumstearat).
4. (4) Ladungssteuerungsteilchen: Metalloxide (z.B. Zinnoxid, Titanoxid, Zinkoxid, Silica, Aluminiumoxid), Carbon Black.

For example, the following are used for the organic or inorganic fine powder.

1. (1) Fluidizers: silica, alumina, titanium oxide, carbon black and fluorinated carbon.
2. (2) Abrasives: metal oxides (e.g. strontium titanate, cerium oxide, aluminum oxide, magnesium oxide, chromium oxide), nitrides (e.g. silicon nitride), carbides (e.g. silicon carbide), metal salts (e.g. calcium sulfate, barium sulfate, calcium carbonate).
3. (3) Lubricants: fluororesin powder (e.g. vinylidene fluoride, polytetrafluoroethylene), metal salts of fatty acids (e.g. zinc stearate, calcium stearate).
4. (4) Charge control particles: metal oxides (e.g. tin oxide, titanium oxide, zinc oxide, silica, aluminum oxide), carbon black.

The organic or inorganic fine powder can be subjected to a surface treatment in order to improve the toner flowability and to ensure a more uniform toner charge. The treating agent for performing hydrophobic treatment of the organic or inorganic fine powder can be exemplified by unmodified silicone varnishes, various modified silicone varnishes, unmodified silicone oils, various modified silicone oils, silane compounds, silane coupling agents, organosilicon compounds other than the above and organotitanium compounds. A single one of these treatment agents can be used or a variety can be used in combination.

The measurement methods involved with the present invention are described below.
Method for observing the toner cross section with a scanning transmission electron microscope (STEM)

The toner cross section for observation with a scanning transmission electron microscope (STEM) is prepared as follows.

The procedure for making the toner cross section is described below.

The toner is first scattered into a single layer on a cover slip (square cover slip, square No. 1, Matsunami Glass Ind., Ltd.), and an Os film (5 nm) and a naphthalene film (20 nm) are covered thereon as a protective film an osmium plasma coater (OPC80T, Filgen, Inc.).

D800 photocurable resin (JEOL Ltd.) is then filled into a PTFE tube (inner diameter 1.5 mm∅ × outer diameter ∅3 mm × 3 mm), and the aforesaid cover slip is carefully placed on the tube with the toner facing to the photo-curable resin D800. This assembly is exposed and the resin is cured, followed by removal of the cover slip and tube to produce a resin cylinder in which the toner is embedded on the outermost surface side.

With an ultrasonic ultramicrotome (UC7, Leica) cross sections of the center of the toner are produced by cutting from the top side of the resin cylinder with a cutting speed of 0.6 mm / s only along the length of the toner radius (e.g. 4.0 µm, when the weight average particle diameter (D4) is 8.0 µm).

Thin section samples of the toner cross section are then produced by cutting with a film thickness of 100 nm. Cross sections of the center of the toner can be obtained by cutting according to this method.

An image is captured using a STEM probe size of 1 nm and an image size of 1024 x 1024 pixels. The image is captured by setting the contrast to 1425 and the brightness to 3750 on the detector control panel for the bright field image, and the contrast to 0.0, the brightness to 0.5, and the gamma to 1.00 the image control panel. The image enlargement is 100,000 times, and the image acquisition is carried out so that it fits about a quarter to half the circumference of the cross section for a toner particle, as in FIG 1 shown.

The organosilicon polymer-containing protruding portions are measured by subjecting the obtained image to image processing using image processing software (Image J (available at https://imagej.nih.gov/ij/)). The image processing is carried out on 30 STEM images.

First, using the line drawing tool, draw a line along the perimeter of the toner base particle (select Segment Line on the Straight tab). In areas where If the protruding portion of the organosilicon polymer is embedded in the toner base particle, the lines are connected seamlessly as if this embedding had not taken place.

The conversion to a flat image is based on this line (selecting Selection in the Edit tab and converting the line width to 500 pixels using Properties, then selecting Selection in the Edit tab and executing Straightener). Using the methodology described above, the protrusion width w, the protrusion diameter D and the protrusion height H are measured at each individual location of an organosilicon polymer-containing protruding portion in the flat image. P (D / w) is calculated from the measurement results of the 30 STEM images. In addition, the cumulative distribution of the supernatant height H is generated and H80 is calculated.

In addition, Σw is used for the sum of the protrusion widths w of the protruding portions with a protrusion height H of 40 nm to 300 nm that are present in the flat image used for the image analysis, and the circumferential length L is for the width of the for the flat image used for image processing. This width of the flat image corresponds to the length of the surface of the toner base particle in the STEM image. Σw / L is calculated for a single image and the arithmetic mean over the 30 STEM images is used.

The details of the measurement of the protruding sections are as in the previous description and in 2 to 4 specified.

The measurement is performed after the scale on the image has been overlaid with Straight Line in the Straight tab in ImageJ and the length of the scale on the image has been set using Set Scale in the Analysis tab. The line segments corresponding to the overhang width w and the overhang height H are drawn with a straight line in the Straight tab, and the measurement can be performed using Measure in the Analysis tab.

Method for calculating the average particle diameter of protruding sections using a scanning electron microscope (SEM)

The SEM observation procedure is as follows. This is done on the image taken using an S-4800 ultra-high resolution field emission scanning electron microscope from Hitachi (Hitachi High-Technologies Corporation). The conditions for image acquisition using S-4800 are as follows.

sample preparation

A conductive paste (Product No. 16053, PELCO Colloidal Graphite, Isopropanol Base, TED PELLA, Inc.) is thinly coated on the sample rack (15 mm × 6 mm aluminum sample rack) and the toner is sprayed on it. After excess toner is removed from the sample rack using an air blower, platinum vapor deposition is performed at 15 mA for 15 seconds. The sample rack is inserted into the sample holder and the height of the sample rack is set to 30 mm using the sample height indicator.

Setting the observation conditions with S-4800

Liquid nitrogen is placed in the edge of the anti-contamination trap attached to the S-4800 housing and left to stand for 30 minutes. The “PC-SEM” of the S-4800 is started and flushing is carried out (the FE tip, which is the electron source, is cleaned). The display area for the acceleration voltage in the control panel on the screen is clicked and the [Flushing] button is pressed to open the flushing execution dialog. A flushing intensity of 2 is confirmed and execution is carried out. The emission current due to flushing is confirmed to be 20 to 40 µA. The sample holder is inserted into the sample chamber of the S-4800 housing. [Home] is pressed on the control panel to bring the sample holder into the observation position.

The display area for the acceleration voltage is clicked to open the dialog for the HV execution dialog, and the acceleration voltage is set to [2.0 kV] and the emission current to [10 µA]. In the [Base] tab of the control panel, the signal selection is set to [SE]; [lower (L)] is selected for the SE detector; and the device is placed in the backscattered electron image observation mode. Similarly, in the [Base] tab of the control panel, the Probe current of the condition block of the electronic optical system set to [Normal], the focus mode to [CLOCK] and WD to [8.0 mm]. The [ON] key in the acceleration voltage display area of the control panel is pressed to apply the acceleration voltage.

focus adjustment

The magnification is set to 5,000X (5k) by dragging within the magnification display area of the control panel. Turning the focus control [COARSE] on the control panel adjusts the aperture orientation when a certain degree of focus has been achieved. Click [Align] on the control panel and the alignment dialog will appear and [Beam] will be selected. The displayed beam is moved to the center of the concentric circles by turning the STIGMA / ALIGNMENT controls (X, Y) on the control panel.

[Aperture] is selected and the STIGMA / ALIGNMENT knobs (X, Y) are rotated sequentially and adjusted to stop the movement of the image or to minimize the movement. The aperture dialog is closed and the focus is done with the autofocus. The focusing is carried out by repeating this process twice. When the center of the main diameter of the observed particle is set to the center of the measurement screen, the magnification by dragging within the magnification display area of the control panel is set to 10,000X (10k). Turning the focus control [COARSE] on the control panel adjusts the aperture orientation when a certain degree of focus has been achieved. Click [Align] on the control panel and the alignment dialog will appear and [Beam] will be selected. The displayed beam is moved to the center of the concentric circles by turning the STIGMA / ALIGNMENT controls (X, Y) on the control panel.

Then [Aperture] is selected and the STIGMA / ALIGNMENT controls (X, Y) are rotated sequentially and adjusted to stop the movement of the image or to minimize the movement. The aperture dialog is closed and the focus is done with the autofocus. The magnification is then set to 50,000X (50k); the focus is adjusted as described above with the focus control and the STIGMA / ALIGNMENT controls; refocusing is done with autofocus. This process is repeated to reach the focus.

image storage

The brightness adjustment is performed using the ABC mode, and a photo of 640 × 480 pixels is taken and saved.

Using the obtained SEM image, the number-average diameter (D1) of the sections at least 20 nm projecting at 500 locations on the toner particle surface is calculated using the image processing software (ImageJ). The measurement procedure is as follows.

• Measure the number average diameter of protruding sections made of organosilicon polymer

The protruding sections and the toner base particles in the image are binarized and differentiated in color by particle analysis. The largest diameter of the selected shape is then selected from the measurement commands and the protruding diameter R (maximum diameter) of the protruding section at one point is measured. This process is carried out several times and the number-average diameter is calculated for the protruding diameter R by determining the arithmetic mean for 500 digits.

Method for measuring the fixation ratio of organosilicon polymer

A sucrose concentrate is prepared by adding 160 g of sucrose (Kishida Chemical Co., Ltd.) to 100 mL of deionized water and dissolving with heating in a water bath. 31 g of this sucrose concentrate and 6 mL Contaminon N (a 10 mass% aqueous solution of a neutral pH-7 detergent for cleaning precision measuring instruments, comprising a non-ionic surfactant, an anionic surfactant and an organic builder, Wako Pure Chemical Industries, Ltd. ) are placed in a centrifugal separation tube (50 mL volume) to produce a dispersion. 1.0 g of the toner is added to this dispersion and clumps of the toner are e.g. dissolved with a spatula.

The centrifugal separation tube is shaken with a shaker for 20 minutes at 350 strokes per minute (spm, stroke per minute). After shaking, the solution is transferred to a glass tube (50 mL volume) for swing rotor operation and separated with a centrifugal separator (H-9R, Kokusan Co., Ltd.) under conditions of 3,500 rpm and 30 minutes. The satisfactory separation of the toner from the aqueous solution is checked visually, and the toner separated into the top layer is recovered using a spatula, for example. The aqueous solution with the recovered toner is filtered on a vacuum filter and then dried in a dryer for at least 1 hour. The dried product is crushed with a spatula and the amount of silicon is measured by X-ray fluorescence. The fixing ratio (%) is calculated from the ratio of the amount of the measured element between the toner after being washed with water and the starting toner.

The measurement of the X-ray fluorescence of the respective element is based on JIS K 0119-1969 and is as follows.

A wavelength-dispersive X-ray fluorescence analyzer "Axios" (PANalytical B.V.) is used as the measuring device and the software "SuperQ ver. 4.0F" (PANalytical B.V.) supplied with the device is used to set the measurement conditions and analyze the measurement data. Rh is used for the X-ray tube anode; a vacuum is used for the measuring atmosphere; the measuring diameter (collimator mask diameter) is 10 mm; and the measurement time is 10 seconds. The detection is carried out with a proportional counter (PC) when measuring the light elements and with a scintillation counter (SC) when measuring the heavy elements.

About 1 g of the starting toner or the toner, after being washed with water, is placed in a special aluminum compression ring with a diameter of 10 mm and smoothed, and with a “BRE-32” tablet compressor (Maekawa Testing Machine Mfg. Co., Ltd.), a pellet is produced by molding to a thickness of about 2 mm at 20 MPa for 60 seconds, and this pellet is used as a measurement sample.

The measurement is carried out under the conditions mentioned above and the elements are identified on the basis of the positions of the resulting X-ray peaks; their concentrations are calculated from the counting frequency (unit: cps), which corresponds to the number of x-ray photons per unit of time.

For example, to quantify the amount of silicon in the toner, 0.5 parts by mass of silica (SiO ₂ ) fine powder is added to 100 parts by mass of the toner particle and mixed thoroughly with a coffee grinder. 2.0 parts by mass and 5.0 parts by mass of the silica fine powder are also mixed with the toner particles and serve as samples for the preparation of calibration curves.

For each of these samples, a pellet of the sample for the preparation of the calibration curve is produced as described above with the tablet compressor, and the count rate (unit: cps) is measured for the Si-Kα radiation which is at a diffraction angle (2θ) = 109, 08 ° with PET for the analyzer crystal is observed. In this case, the acceleration voltage and the current value for the X-ray generator are 24 kV and 100 mA, respectively. A calibration curve in the form of a linear function is obtained by placing the obtained X-ray count rate on the vertical axis and the amount of SiO ₂ addition on the horizontal axis for each calibration curve sample.

The toner to be analyzed is then processed into a pellet using the tablet compressor and subjected to a measurement of its Si-Ka radiation count rate. The content of the organosilicon polymer in the toner is determined from the aforementioned calibration curve. The ratio of the amount of the element in the toner after washed with water to the amount of the element in the starting toner calculated by this method is determined and used as the fixing ratio (%).

Examples

The present invention is specifically described below using examples, but the present invention is not limited to or by these examples. Unless expressly stated otherwise, the "parts" used for the materials in the examples and comparative examples are in all cases on a mass basis.

Toner 1 Production Example

Aqueous medium 1 preparation step

14.0 parts of sodium phosphate (decahydrate, RASA Industries, Ltd.) was placed in 650.0 parts of deionized water in a reactor with an agitator, thermometer and reflux condenser, and this was kept at 65 ° C for 1.0 hours while using nitrogen was rinsed.

An aqueous calcium chloride solution of 9.2 parts of calcium chloride (dihydrate) dissolved in 10.0 parts of deionized water was introduced all at once while stirring at 15,000 rpm with a TK homomixer (Tokushu Kika Kogyo Co., Ltd.) to prepare aqueous medium containing a dispersion stabilizer. 10 mass% hydrochloric acid was introduced into the aqueous medium to adjust the pH to 5.0, and so was the aqueous medium 1 to obtain.
Step of preparing the polymerizable monomer composition • styrene: 60.0 parts CI Pigment Blue 15: 3: 6.5 parts

These materials were placed in an attritor (Mitsui Miike Chemical Engineering Machinery Co., Ltd.) and dispersed with zirconium oxide particles of 1.7 mm in diameter for 5.0 hours at 220 rpm to prepare a pigment dispersion. The following materials were added to this pigment dispersion. • styrene: 20.0 parts N-butyl acrylate: 20.0 parts Crosslinker (divinylbenzene): 0.3 parts • saturated polyester resin: 5.0 parts (Polycondensate of propylene oxide-modified bisphenol A (2 mol adduct) and terephthalic acid (10: 12 mol ratio), glass transition temperature Tg = 68 ° C, weight-average molecular weight Mw = 10,000, molecular weight distribution Mw / Mn = 5.12) • Fischer-Tropsch wax (melting point: 78 ° C): 7.0 parts

This was kept at 65 ° C and a polymerizable monomer composition was prepared by dissolving and dispersing for uniformity with a T.K. homomixer (Tokushu Kika Kogyo Co., Ltd.) at 500 rpm.

granulation

While maintaining the temperature of the aqueous medium 1 at 70 ° C and the rotation speed of the TK homomixer at 15,000 rpm, the polymerizable monomer composition was put into the aqueous medium 1 introduced and 10.0 parts of the polymerization initiator t-butyl peroxypivalate added. The granulation was carried out with the stirrer for 10 minutes while maintaining 15,000 rpm.

· Polymerization distillation step

After the granulation step, the stirrer was switched to a propeller wheel and polymerization was carried out for 5.0 hours while maintaining 70 ° C. and stirring at 150 rpm. The temperature was then raised to 85 ° C and the polymerization reaction was carried out under heating for 2.0 hours.

The reflux condenser on the reactor was then switched to a condenser, and distillation was carried out for 6 hours by heating the slurry to 100 ° C, thereby distilling off the unreacted polymerizable monomer and obtaining a toner base particle dispersion.

Polymerization of organosilicon compound

60.0 parts of deionized water were metered into a reactor with a stirrer and thermometer and the pH was adjusted to 4.0 with 10% by mass of hydrochloric acid. This was heated with stirring to bring the temperature up to 40 ° C. 40.0 parts of the organosilicon compound methyltriethoxysilane was then added and hydrolysis was carried out for at least 2 hours with stirring. The end point of the hydrolysis was confirmed by visual observation when there was no oil-water separation and a layer was present; Cooling then gave an organosilicon compound hydrolysis solution.

After the obtained toner base particle dispersion was cooled to 55 ° C, 25.0 parts of the hydrolysis solution of the organosilicon compound was added and polymerization of the organosilicon compound was initiated. Holding in this state was carried out for 15 minutes, followed by adjusting the pH to 5.5 with a 3.0% aqueous sodium bicarbonate solution. A hold was carried out at 55 ° C for 60 minutes with continued stirring, after which the pH was adjusted to 9.5 with a 3.0% aqueous sodium bicarbonate solution, followed by an additional hold for 240 minutes to obtain a toner particle dispersion ,

Washing and drying step

After completing the polymerization step, the toner particle dispersion was cooled; hydrochloric acid was added to the toner particle dispersion to adjust the pH to 1.5 or below; Holding was performed with stirring for 1 hour; and the solid-liquid separation was carried out on a pressure filter to obtain a toner cake. This was reslurried with deionized water to obtain another dispersion, followed by solid-liquid separation on the above filter to obtain a toner cake.

The resulting toner cake was dried in a thermostated chamber at 40 ° C for 72 hours and classified into a toner particle 1 to obtain. The conditions for the production of toner particles 1 are given in Table 1. [Table 1] Toner Particle No. Type of organosilicon compound added amount hold time Condensation reaction 1 Condensation reaction 2 Temperature ° C Remarks pH pH pH time 1 methyltriethoxysilane 10 0.25 5.5 1.0 9.5 4.0 55 2 methyltriethoxysilane 12 0.25 5.5 1.0 9.5 4.0 55 3 methyltriethoxysilane 16 0.25 5.5 1.0 9.5 4.0 55 4 methyltriethoxysilane 10 0.25 7.0 1.5 9.5 3.5 55 5 methyltriethoxysilane 12 0.25 7.0 1.5 9.5 3.5 55 6 methyltriethoxysilane 16 0.25 7.0 1.5 9.5 3.5 55 7 methyltriethoxysilane 12 0.25 7.0 3.5 9.5 1.5 55 8th methyltriethoxysilane 16 0.25 4.0 1.0 9.5 3.5 55 9 methyltriethoxysilane 16 0.25 4.0 2.0 9.5 3.0 55 10 methyltrimethoxysilane 10 0.50 5.5 1.0 9.5 4.0 55 11 Methyltriethoxysilane / tetraethoxysilane 9.5 / 0.5 0.50 5.5 1.0 9.5 4.0 55 12 Methyltriethoxysilane / vinyltriethoxysilane 9.0 / 1.0 0.50 5.5 1.0 9.5 4.0 55 C. 1 methyltriethoxysilane 5 1.00 9.5 5.0 - - 70 Sol-gel silica was also used when the organosilicon compound was added. C. 2 3- (methacryloxy) propyltrimethoxysilane 30 5.00 9.5 10.0 - - 70 C. 3 none used - - - - - - no organosilicon compound was used.

In the table, “C.” denotes the comparison, the unit of time is h (hours), and the “addition amount” is the addition amount (parts) of the organosilicon compound in the step of polymerizing the organosilicon compound.

Toner particles 2 to 12 manufacturing process

The toner particles 2 to 12 by a procedure similar to that of the toner particle 1 received, but changed to the conditions shown in Table 1.

Comparative Toner Particle 1 Manufacturing Process

It became a comparison toner particle 1 obtained, wherein the polymerization of the organosilicon compound was changed as described below. Polymerization of organosilicon compound

60.0 parts of deionized water were metered into a reactor with a stirrer and thermometer and the pH was adjusted to 4.0 with 10% by mass of hydrochloric acid. This was heated with stirring to bring the temperature up to 40 ° C. 40.0 parts of the organosilicon compound methyltriethoxysilane was then added and hydrolysis was carried out for at least 2 hours with stirring. The end point of the hydrolysis was confirmed by visual observation when there was no oil-water separation and a layer was present; Cooling then gave an organosilicon compound hydrolysis solution.

The temperature of the resulting toner base particle dispersion was cooled to 70 ° C and the pH was then adjusted to 9.5 with a 3.0% aqueous sodium bicarbonate solution. With continued stirring at 70 ° C., 5.0 parts of colloidal silica (Snowtex ST-ZL, solids content = 40%) and 12.5 parts of the hydrolysis solution of the organosilicon compound were added and the polymerization of the organosilicon compound was initiated. This was held as it is for 300 minutes to obtain a toner particle dispersion.

Comparative Toner Particle 2 Manufacturing Process

Comparative Toner 2 by a procedure similar to the toner particle 1 obtained, but changing the polymerization for the organosilicon compound as indicated below. Polymerization of organosilicon compound

A mixed medium was prepared by dissolving 1.0 part of polyvinyl alcohol in 20 parts of a mixed solvent of ethanol / water = 1: 1 (mass ratio), and this mixed medium was dispersed in the toner base particle dispersion. 30 parts of the silicon compound 3- (methacryloxy) propyltrimethoxysilane was then dissolved and stirring was continued for an additional 5 hours to induce swelling and incorporation into the toner particle by the 3- (methacryloxy) propyltrimethoxysilane.

Then, after the temperature was brought to 70 ° C, the pH was adjusted to 9.5 with a 3.0% aqueous sodium bicarbonate solution. A sol-gel reaction was developed on the toner particle surface by stirring at room temperature for 10 hours, thereby reducing the comparison toner particle 2 was obtained.

Comparative Toner Particle 3 Manufacturing Process

A comparison toner particle 3 was obtained by polymerizing the organosilicon compound in the manufacturing example for toner particles 1 was not carried out.

example 1

toner particles 1 what it's like as a toner 1 used, and the following durability assessments of transferability and contamination of elements were made. The results are shown in Table 2. [Table 2] Toner Particle No. Results of the analysis of the STEM image R nm X-ray fluorescence analysis results P (D / w)% by number Σw / L H80 nm Amount of silicon (mass%) Fixation ratio% Toner 1 1 89% 0.61 75 45 3.5 99 Toner 2 2 85% 0.60 80 40 4.3 98 Toner 3 3 82% 0.64 85 45 5.3 97 Toner 4 4 76% 0.33 80 30 3.6 99 Toner 5 5 72% 0.40 85 35 4.4 98 Toner 6 6 73% 0.42 90 40 5.4 95 Toner 7 7 90% 0.30 90 25 4.4 91 Toner 8 8th 95% 0.83 75 60 5.4 84 Toner 9 9 85% 0.91 70 65 5.3 94 Toner 10 10 90% 0.62 80 40 3.4 94 Toner 11 11 87% 0.45 90 40 3.5 92 Toner 12 12 95% 0.85 70 55 3.4 99 Comparative Toner 1 C. 1 0% 0.75 65 60 5.3 92 Comparative Toner 2 C. 2 20% 0.20 45 30 3.5 78 Comparative Toner 3 C. 3 40% 0.20 75 180 4.4 68 Comparative Toner 4 C. 3 0% 0.30 60 80 4.2 85

In the table, “C.” denotes the comparison and “R” denotes the number-average diameter for the protruding diameter R (nm).

Procedure for assessing durability

An LBP7700C, a commercial laser printer from Canon, Inc., was used in a modified form. The modification consisted in providing the development roller with a rotation speed of 360 mm / sec by exchanging the main unit of the evaluation machine and changing the software.

The toner was placed in a toner cartridge for the LBP7700C, and this toner cartridge was kept in an environment of normal temperature and humidity NN (25 ° C / 50% RH) for 24 hours. After standing in this environment for 24 hours, the toner cartridge was installed in the above-mentioned device.

In order to evaluate the transferability and contamination of elements, 7,500 prints of an image with a printing proportion of 5.0% in the NN environment were printed in the transverse direction in the middle of the A4 paper with a 50 mm margin on both the left and right , The assessments were made after the initial print and after the output of 7,500 prints.

Assessment of transferability

The transferability (untransferred density) was evaluated as follows. A solid image was output, and the untransferred toner on the photosensitive member during the formation of the solid image was peeled off by sticking with a transparent polyester adhesive tape. A density difference was calculated by subtracting from the density for the peeled tape only the density of the tape adhered to paper. The density measurement was carried out at five points and the mean value was determined. This density difference value was classified as follows.

The density was measured with an X-Rite color reflection densitometer (X-Rite 500 series, X-Rite, Incorporated). AC or better was considered excellent.

assessment criteria

• A: the density difference is less than 0.030
• B: the density difference is at least 0.030 but less than 0.050
• C: the density difference is at least 0.050 but less than 0.100
• D: the density difference is equal to or greater than 0.100

Assessment of element contamination

The contamination of elements (stability of full tone / halftone gradation stability) was evaluated as follows.

First, an image control drum unit was prepared. A toner evaluation loading roller was then installed on the image control drum unit and the image output was carried out. An image was produced for the image in which a halftone was printed over the entire page. The density was measured on the image produced by the durability test in the middle area of the halftone image and in the 50 mm edges to the right and left, and the judgment was made based on the density difference between the edge area and the middle area.

It is known that when the charging element is contaminated, an uneven charge is generated on the photosensitive element and that an uneven image density is then produced in the halftone image (HT image).

The density was measured with an X-Rite color reflection densitometer (X-Rite 500 series, X-Rite, Incorporated). AC or better was considered excellent.

assessment criteria

• A: The density difference for the halftone after the output of 7,500 prints is less than 0.030
• B: The density difference for the halftone after the output of 7,500 prints is at least 0.030 but less than 0.050
• C: The density difference for the halftone after the output of 7,500 prints is at least 0.050 but less than 0.100
• D: The density difference for the halftone after the output of 7,500 prints is equal to or greater than 0.100

The results of toner durability evaluations 1 are shown in Table 3. [Table 3] Example No. Toner No. Assessment of transferability Assessment of element contamination initial after 7,500 prints after 7,500 prints rating density not transferred rating density not transferred rating HT density non-uniformity 1 1 0.016 A 0,022 A 0,012 A 2 2 0,014 A 0.024 A 0.016 A 3 3 0,012 A 0.024 A 0,012 A 4 4 0.016 A 0.078 C 0,040 B 5 5 0,012 A 0.032 B 0,070 C 6 6 0,006 A 0.062 C 0,080 C 7 7 0,014 A 0.062 C 0.034 B 8th 8th 0.024 A 0.032 B 0.019 A 9 9 0.034 B 0,042 B 0.011 A 10 10 0.016 A 0,022 A 0,020 A 11 11 0.016 A 0,022 A 0,040 B 12 12 0.032 B 0,042 B 0.032 B CE 1 C. 1 0,020 A 0,102 D 0.118 D CE 2 C. 2 0,150 D 0.370 D 0.276 D CE 3 C. 3 0.098 C 0,350 D 0.306 D CE 4 C. 4 0,052 C 0.506 D 0,324 D

In the table, "C." stands for comparison and "C.E." for comparison example.

Assessment of toners 2 through 12 and comparative toners 1 through 4

toner particles 2 to 12 and comparison toner particles 1 and 2 were as they are as toners 2 to 12 and comparison toner 1 and 2 used and the assessments were made on it.

For the comparison toner 3 and 4 the toners were made by performing external addition on comparative toner particles 3 manufactured under the following conditions, followed by the assessments.

• Production of comparison toner 3

An organosilicon fine particle A was first synthesized as described below.

An aqueous solution was prepared by introducing 500 g of deionized water into a reactor and adding 0.2 g of a 48% aqueous sodium hydroxide solution. 65 g of methyltrimethoxysilane and 50 g of tetraethoxysilane were added to this aqueous solution; a hydrolysis reaction was carried out for 1 hour while the temperature was kept at 13 ° C to 15 ° C; 2.5 g of a 20% aqueous solution of sodium dodecylbenzenesulfonate were added; and a hydrolysis reaction was carried out at the same temperature for 3 hours. A transparent reaction product containing silanol compounds was obtained in about 4 hours.

A condensation reaction was then carried out for 5 hours while the temperature of the obtained reaction product was kept at 70 ° C to obtain an aqueous suspension containing fine particles of an organosilicon compound. This aqueous suspension was filtered on a membrane filter; the filtrate was fed to a centrifugal separator; and white fine particles were separated. The separated white fine particles were washed with water and subjected to hot air drying at 150 ° C. for 5 hours to obtain organosilicon fine particles A.

Observation of the organosilicon fine particle A with a scanning electron microscope showed that this organosilicon fine particle A was a hollow hemispherical body, and the calculation of the number-average particle diameter (“μm”) for the long diameter and the short diameter of the hemisphere gave 180 nm for the long diameter and 80 nm for the short diameter.

3.0 parts of organosilicon fine particles A became 100 parts of the comparison toner 3 added and mixed with a Henschel mixer with a peripheral speed for the stirring blade of 20 m / s. Comparative toner 3 was then made by mixing 1.5 parts of hexamethyldisilazane treated hydrophobic silica having a number average particle diameter of 12 nm with a Henschel mixer at a peripheral speed for the stirring blade of 20 m / s.

• Production of comparison toner 4

Comparative toner 4 became like when making the comparison toner 3 , but with the following changes: The organosilicon fine particle A was changed to a hydrophobic sol-gel silica (number average particle diameter = 80 nm, Nippon Aerosil Co., Ltd.), and the circumferential stirring blade speed for the Henschel mixer became 20 m / s changed to 40 m / s.

The analysis results for each toner are shown in Table 2 and the results for the durability evaluations are shown in Table 3.

Although the present invention has been described with reference to exemplary embodiments, it should be understood that the invention is not limited to the disclosed exemplary embodiments. The scope of the following claims is to be interpreted as far as possible to cover all these changes as well as equivalent structures and functions.

QUOTES INCLUDE IN THE DESCRIPTION

This list of documents listed by the applicant has been generated automatically and is only included for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Patent literature cited

• JP 2009036980 A [0005, 0010, 0012]
• JP 2001075304 A [0008, 0013]
• JP 2017138462 A [0009, 0014]
• JP 2008257217 A [0011, 0012]

Claims (5)

A toner comprising: a toner particle containing a toner base particle and an organosilicon polymer present on a surface of the toner base particle, the organosilicon polymer having the structure represented by the following formula (1); the organosilicon polymer forms protruding portions on the surface of the toner base particle; and in a flat image provided by observing the toner cross section with a scanning transmission electron microscope STEM, drawing a line along the circumference of the toner base particle surface and converting based on this line along the circumference, and the length of the line is assumed to be along the circumference for a segment where a protruding portion and the toner base particle form a continuous interface, is taken as the protrusion width w, the maximum length of a protruding portion in the direction perpendicular to the protrusion width w is taken as the protrusion diameter D and that Length in the line segment which forms the protrusion diameter D, from the tip of a protruding section to the line along the circumference, is taken as the protrusion height H, the numerical component P (D / w), in protruding sections with a protrusion Height H from 40 nm to 300 nm, from protruding n sections with a ratio D / w of the protrusion diameter D to the protrusion width w from 0.33 to 0.80, at least 70% by number. R-SiO _3/2 (1) wherein in the formula R represents an alkyl group with 1 to 6 carbon atoms or a phenyl group. Toner after Claim 1 , wherein when observing the toner cross section using a scanning transmission electron microscope STEM, assuming that the width of the flat image is taken as the circumferential length L and the sum of the overhang widths w of the protruding sections with an overhang height H of 40 nm to 300 nm of the protruding portions of the organosilicon polymer present in the flat image is taken as Σw, Σw / L is from 0.30 to 0.90. Toner after Claim 1 or 2 wherein the fixing ratio of the organosilicon polymer on the toner is at least 80% by mass. Toner according to any of the Claims 1 to 3 where H80 is at least 65 nm, where if a cumulative distribution of the supernatant height H is made for the protruding sections with a supernatant height H of 40 nm to 300 nm, H80 is the supernatant height which is 80% by number corresponds to the accumulation of the overhang height H from the small side. Toner according to any of the Claims 1 to 4 where R is an alkyl group having 1 to 6 carbon atoms.

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